Composite 3D-printed reactors for gas absorption, purification, and reaction

ABSTRACT

A composite material for gas capture including CO2 capture and capture of other gases. The composite material includes solid or liquid reactive material, filler material, and a gas-permeable polymer coating such that the reactive material forms micron-scale domains in the filler material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 15/468,297 filed Mar. 24, 2017 titled composite 3D-printedreactors for gas absorption, purification, and reaction which isincorporated by reference herein.

STATEMENT AS TO RIGHTS TO APPLICATIONS MADE UNDER FEDERALLY SPONSOREDRESEARCH AND DEVELOPMENT

The United States Government has rights in this application pursuant toContract No. DE-AC52-07NA27344 between the United States Department ofEnergy and Lawrence Livermore National Security, LLC for the operationof Lawrence Livermore National Laboratory.

BACKGROUND Field of Endeavor

The present application relates to reactors for gas absorption,purification, and/or reaction and more particularly to composite 3-Dprinted reactors for gas absorption, purification, and/or reaction.

State of Technology

This section provides background information related to the presentdisclosure which is not necessarily prior art.

The exchange of gas into or out of a liquid is a common problem in theabsorption of gases into a solvent for industrial chemical processes,gas purification, and water purification. The potentially largest scaleapplication is for the absorption of CO₂ for carbon capture and storagefrom power plants. Other applications include purification of naturalgas, purification of biogas, and various industrial gas-to-liquidreactions. The most common method for gas absorption is the use of a“packed tower” absorption column. The absorption column is typically acylindrical reactor filled with a packing material. Liquid solvent ispumped to the top of the tower and allowed to flow down over the packingwhile gas is blown from the bottom of the tower in the oppositedirection. The liquid solvent forms a film over the wetted parts of thepacking material, resulting in a gas-liquid interface where the exchangebetween CO₂ and solvent takes place.

A major limitation of these tower packings is that the surface-area tovolume ratio of the liquid is limited by the thickness of the liquidfilm. This thickness is determined by the properties of the solvent, butis typically around 1 mm. Additional area can be put into the towerusing finer packings, but this leads to higher holdup of liquid, andimpeded gas flow.

Solid sorbents are an alternative to liquid solvents in manyapplications, including large-scale CO₂ capture. Solid sorbents arepreferred for air purification for, e.g. small submarines and personalunderwater rebreathers and removal of volatile organic compounds emittedfrom certain industrial processes. Solid sorbents include mineral CO₂sorbents like soda-lime, designer gas sorbents like metal-organicframeworks (MOFs), zeolites, and activated carbons. Solid sorbents aretypically prepared in a powder, and must be pelletized or formed intomonoliths with a binder, reducing accessible surface area and yieldingsub-optimal gas flow.

SUMMARY

Features and advantages of the disclosed apparatus, systems, and methodswill become apparent from the following description. Applicant isproviding this description, which includes drawings and examples ofspecific embodiments, to give a broad representation of the apparatus,systems, and methods. Various changes and modifications within thespirit and scope of the application will become apparent to thoseskilled in the art from this description and by practice of theapparatus, systems, and methods. The scope of the apparatus, systems,and methods is not intended to be limited to the particular formsdisclosed and the application covers all modifications, equivalents, andalternatives falling within the spirit and scope of the apparatus,systems, and methods as defined by the claims.

The inventor's apparatus, systems, and methods provide a compositematerial for gas capture, notably CO₂ capture and storage. The compositematerial includes a mixture of a solid or liquid reactive filler and agas-permeable polymer (e.g. silicone), such that the reactive fillerforms micron-scale domains in the polymer matrix. In contrast to typicalabsorption schemes based on liquid solvents or solid sorbent powders,the composite materials can be fabricated into arbitrary fixed shapesvia additive or conventional manufacturing. The gas-permeable polymermatrix acts as a gas-permeable support while the reactive filler acts asa gas sorbent or catalyst for chemical reactions. Control over thematerial shape allows for the patterning of high surface-area-to-volumeratio structures for fast reactivity while minimizing pressure dropstypically associated with high surface area materials and packings. Theinventor's apparatus, systems, and methods can be used for theabsorption of gases or catalyzing chemical reactions involving a gas.This use can be tailored for specific applications such as CO capturefrom power plants, CO₂ utilization, natural gas purification, biogaspurification, and underwater rebreather applications. Specific gases andreactions can be targeted using different reactive fillers.

In various embodiments, the inventor's apparatus, systems, and methodsprovide a method of making a reactor for removing a single gas ormultiple gases from a gas stream containing the single gas or themultiple gases using the steps of providing a filler material, providinga sorbent material, extruding the filler material and the sorbentmaterial to produce an extrudant, and providing a gas-permeable polymercoating layer around the extrudant to produce the reactor. The reactorincludes an extruded composite; a filler in the extruded composite;units of sorbent material in the extruded composite with the filler; anda gas-permeable polymer coating layer around the extruded composite.

The apparatus, systems, and methods are susceptible to modifications andalternative forms. Specific embodiments are shown by way of example. Itis to be understood that the apparatus, systems, and methods are notlimited to the particular forms disclosed. The apparatus, systems, andmethods cover all modifications, equivalents, and alternatives fallingwithin the spirit and scope of the application as defined by the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and constitute apart of the specification, illustrate specific embodiments of theapparatus, systems, and methods and, together with the generaldescription given above, and the detailed description of the specificembodiments, serve to explain the principles of the apparatus, systems,and methods.

FIG. 1 is a flow chart illustrating one embodiment of the inventor'sapparatus, systems, and methods.

FIG. 2 illustrates one embodiment of the inventors' ink that can be usedto create a monolith reactor.

FIG. 3 an embodiment of the inventor's 3D printing and otherwisemanufacturing of a monolithic reactor is illustrated.

FIG. 4 illustrates an embodiment of the inventor's monolith reactor.

FIG. 5 illustrates spheres containing liquid stripping solvent forcarbon dioxide removal.

FIG. 6 is an illustration of a system for making the spheres.

FIG. 7 illustrates another embodiment of the inventors' ink that can beused to create a monolith reactor.

FIG. 8 is an illustration of an additive manufacturing system for makingan embodiment of the monolithic reactor.

FIG. 9 illustrates an embodiment of a system utilizing the inventor'sreactor for removing the target gas from a fluid or mixture andregenerating the reactor.

FIG. 10 illustrates another embodiment of the reactor.

FIG. 11 illustrates an embodiment of a reactor stack.

FIG. 12 illustrates an embodiment of the inventor's reactor with acoating layer.

FIG. 13 illustrates an embodiment of the inventor's reactor as a thinsheet rolled up.

FIG. 14 illustrates an embodiment of the inventor's reactor as arandomly entangled mass of filaments.

FIG. 15 illustrates an embodiment of the inventor's reactor as a thinsheet of porous mesh-like or lace-like structure.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

Referring to the drawings, to the following detailed description, and toincorporated materials, detailed information about the apparatus,systems, and methods is provided including the description of specificembodiments. The detailed description serves to explain the principlesof the apparatus, systems, and methods. The apparatus, systems, andmethods are susceptible to modifications and alternative forms. Theapplication is not limited to the forms disclosed. The applicationcovers all modifications, equivalents, and alternatives falling withinthe spirit and scope of the apparatus, systems, and methods as definedby the claims.

The inventor's apparatus, systems, and methods provide ahigh-surface-area, hierarchically-structured, reactive compositematerial for energy-efficient gas purification and the techniques tofabricate this material. The hierarchy consists of, on the one hand,micron-scale domains of solvent or sorbent particles embedded within agas-permeable polymer to form the composite material and, on the otherhand, the submillimeter-scale structures that the composite materialsform to create a monolith reactor. The reactor has channels for optimalgas flow and features sized for fast reaction with the gas. Thestructure optionally consists of hollow tubes where a second solvent,for heat exchange or additional chemical reaction, is flowed through thetube cores.

The reactor is fabricated by dispersing solid sorbents, solid precursorsto liquid solvents, or microencapsulated liquid solvents within a3D-printable, gas-permeable polymer, and then printing or otherwiseshaping the mixture into reactor structures. The composite material maycontain other reactive components, such as a pH-indicator dye to givevisual indication of CO₂ absorption. Various structures can be printedthat have desired properties for gas flow, fit into desired reactorhousings, or provide other benefits. Features at the centimeter orlarger scale can be incorporated into the printed structure, such as ahierarchy of gas channel sizes. The inventors have shown that theresulting structures absorb CO₂ much faster than comparable films of theliquid solvent, indicating much smaller and more efficient reactors arepossible using the printed composite concept than with conventionaltechnology. The CO₂ absorption rates are higher for smaller filamentsizes (which have higher surface area-to-volume ratios) and theyapproach or exceed the absorption rates for the microencapsulatedsolvents we have previously developed. Though the inventors' researchfocus is on CO₂ capture and early demonstrations use sodium carbonate.This invention is widely applicable to other solvents, other reactions,and other applications involving gas purification or heterogeneousreactions involving a gas.

Several key innovations underpin the inventor's apparatus, systems, andmethods:

1. The method of preparing a gas-absorbing composite material, i.e. bymixing solid precursors to liquid solvents with a gas-permeable polymerprecursor, cross-linking the polymer, and then hydrating the solidparticles to form micro-scale solvent domains. This innovation is notspecific to 3-D printing (it can be achieved by extrusion or otherconventional manufacturing techniques), but it is specific to solventsthat can be dispersed as solid powders and then re-hydrated, solidsorbents, or microencapsulated solvents.

2. The concept of preparing and 3-D printing a gas-absorptive ink into amonolith reactor with beneficial gas-flow features. This innovation isnot specific to liquid solvents and can be applied to absorptive orreactive powders that remain solid, such as metal-organic frameworks.

3. The formation of a composite material as in concepts 1 or 2 intohollow-tube structures, where a second liquid is flowed through thecenter of the tubes for the purpose of heat exchange. The tubes can beprinted with a Direct Ink Write 3-D printing system equipped withcore-shell nozzles for printing hollow or liquid-filled tubes.

Referring now to the drawings, and in particular to FIG. 1, anembodiment of the inventor's apparatus, systems, and methods is shown.This embodiment is designated generally by the reference numeral 100.The inventor's apparatus, systems, and methods 100 provide ahigh-surface-area, hierarchically-structured, reactive compositematerial for energy-efficient gas purification and the techniques tofabricate this material. The hierarchy consists of, on the one hand,micron-scale domains of solvent or sorbent particles embedded within agas-permeable polymer to form the composite material and, on the otherhand, the submillimeter-scale structures that the composite materialsform to create a monolith reactor. The reactor has channels for optimalgas flow and features sized for fast reaction with the gas. Thestructure optionally consists of hollow tubes where a second solvent,for heat exchange or additional chemical reaction, is flowed through thetube cores.

A flow chart illustrates the inventor's apparatus, systems, and methods100. The flow chart illustrates a number of individual steps thatencompass the inventor's apparatus, systems, and methods 100.

Step 102 comprises selecting the sorbents. For example, the sorbents canbe mixing solid precursors to liquid solvents with a gas-permeablepolymer precursor, cross-linking the polymer, and then hydrating thesolid particles to form micro-scale solvent domains.

Step 104 comprises dispersing the sorbent material within a 3D printablegas permeable polymer. The inventor's apparatus, systems, and methodsare not specific to liquid solvents and can be applied to absorptive orreactive powders that remain solid, such as metal-organic frameworks.

Step 106 comprises 3-D printing and shaping the sorbent material withina 3D printable gas permeable polymer into a monolith reactor withbeneficial gas-flow features. The inventor's apparatus, systems, andmethods are limited to specific to 3-D printing (it can be achieved byextrusion or other conventional manufacturing techniques), but it isspecific to solvents that can be dispersed as solid powders and thenre-hydrated, solid sorbents, or microencapsulated solvents.

Step 108 comprises curing the monolith reactor by thermal treatment.

Referring now to FIG. 2, one embodiment of the inventors' ink that canbe used to create a monolith reactor is shown. This embodiment of theinventors' ink is designated by the reference numeral 200. The ink 200includes sodium carbonate particles 202 in uncured silicone oil 204. Thesodium carbonate particles 202 were produced by milling solid sodiumcarbonate to a fine powder of ˜10-micron average diameter. The sodiumcarbonate particles 202 were then mixed with an uncured silicone oil204, for example (e.g. Dow Corning® SE1700) via planetary mixing. Theresulting ink 200 was supplied to a Direct Ink Write device for 3-Dprinting into desired structures. The completed structure was thencured. The sodium carbonate particles 202 can be considered solidparticles for some operations and the sodium carbonate particles 202 canbecome liquid units when the sodium carbonate is exposed to moisture.

Referring now to FIG. 3, an embodiment of the inventor's 3D printing andotherwise manufacturing of a monolithic reactor is illustrated. Asillustrated in FIG. 3, extruded material 304 is deposited on a surface310 to be printed by print head 302. For example, the extruded material304 can be composed of the ink illustrated in FIG. 2.

The print head 302 extrudes the material 304 onto the surface 310.Movement of the print head 302 is controlled by computer controller 308which provides freedom of movement along all axes as indicated by thearrows 309. The instructions for creating the reactor 312 is fed to thecomputer controller 308. The computer controller 308 uses theinstructions to move the print head 302 through a series of momentsalong the surface 310 forming the reactor 312.

Referring now to FIG. 4 an embodiment of the inventor's monolith reactoris illustrated. This embodiment is designated generally by the referencenumeral 400. The reactor 400 has channels 402 for optimal gas flow andfeatures sized for fast reaction with the gas. The structure can also beoptionally constructed to consist of hollow tubes where a secondsolvent, for heat exchange or additional chemical reaction, is flowedthrough the tube cores.

As illustrated in FIG. 4, individual channels 402 are made by the shapeof the structure 404. The structure is made of micron-scale domains ofsolvent and/or sorbent particles embedded within a gas-permeable polymerto form the monolith reactor. The structure 404 includes gas-permeableparticles 406 and a solvent matrix 408. This an embodiment 400 of theinventor's monolith reactor is a lattice like structure. The physicaldimensions can be varied by length, width, and height. A smallerfilament size yields a higher surface to volume ratio and faster CO₂absorption rates.

The inventors' ink that is used to create a monolith reactor includessolid or liquid reactive filler and a gas-permeable polymer, such thatthe reactive filler forms micron-scale domains in the polymer matrix.The solid particle reactive filler is illustrated in FIGS. 2 and 4.

Referring now to FIG. 5, one embodiment of the inventors' liquidreactive filler is illustrated. The inventors' liquid reactive fillerutilizes individual spheres that are capsules with liquid strippingsolvents for absorbing CO₂ encapsulated within the capsules. One of thecapsules 500 is shown in FIG. 5. The capsule 500 has a polymer surfacelayer 504 that is permeable to carbon dioxide. A liquid strippingsolvent 502 for absorbing CO₂ is encapsulated within the polymer surfacelayer 504 of the spheres 500.

Referring now to FIG. 6, a system for making the spheres is illustrated.The system for making the spheres is designated generally by thereference numeral 600. The individual spheres have a polymer surfacelayer that is permeable to carbon dioxide and have liquid strippingsolvents for absorbing carbon dioxide encapsulated within the polymersurface layer and inside the spheres.

One specific example of a system for making the spheres is shown in FIG.6. The schematically illustrated method 600 is composed of the followingitems. An injection tube 602 with a ID (um) and OD 1000 (um), acollection tube 604 with an ID of 500 (um) and OD 1000 (um) and an outertube 606 of square cross section with ID of 1000 (um) and ID of 1200(um).

In operation, the inner fluid 610 (Monoethanolamine/H₂O) with aviscosity of 10-50 (cP) and a flow rate of 200-800 (uLh-1) flows in theinjection tube 602 in the direction indicated by the inner fluid arrow.As this fluid proceeds it passes thru a droplet forming nozzle 624. Theformed droplet 626 is released from the nozzle 602 and becomes encasedin the middle fluid 612 (Norland Optical Adhesive Pre-polymer) with aviscosity of 10-50 (cP) and flow rate of 200-800 (uLh-1), the middlefluid 612 is flowing in the direction indicated by arrow 616. The innerfluid droplet 626 becomes encased in the middle fluid 612 formingencapsulated microcapsules 618 that have a CO₂ capturing solvent corewith a thin CO₂ permeable outer shell. The outer fluid (PolyvinylAlcohol Stabilizer) with a viscosity of 10-50 (cP) and a flow rate of200-800 (uLh-1) flowing in the outer tube 606 in the direction indicatedby arrow 622. This outer fluid 620 carries the fabricated microcapsules618 into the collection tube 604. There is a boundary layer 614 thatprevents the middle fluid 612 and outer fluid 620 from mixing as theyhave a large difference in both their viscosity and flow rates. Theabove described method will produce Microcapsules of a controlled sizewith an inner fluid (solvent/catalyst) enclosed in a CO₂ permeablepolymer shell. The fabricated microcapsules 618 move out of the systemas indicated by arrow 628.

Referring now to FIG. 7, another embodiment of the inventors' ink thatcan be used to create a monolith reactor is shown. This embodiment ofthe inventors' ink is designated by the reference numeral 700. The ink700 includes spherical capsules 702 in a gas-permeable polymer 704. Thespherical capsules 700 have a polymer surface layer that is permeable tocarbon dioxide and a liquid stripping solvent for absorbing CO₂encapsulated within the polymer surface layer. The resulting ink 700 canbe supplied to a Direct Ink Write device for 3-D printing into desiredstructures.

Referring now to FIG. 8, another embodiment of the inventors' 3-Dprinting for manufacturing a monolithic reactor is illustrated. Asillustrated in FIG. 8, extruded material 804 is deposited on a surface810 to be printed by print head 802. For example, the extruded material804 can be composed of the ink illustrated in FIG. 7.

The print head 802 extrudes the material 804 onto the surface 810.Movement of the print head 802 is controlled by computer controller 808which provides freedom of movement along all axes as indicated by thearrows 809. The instructions for creating the reactor 812 is fed to thecomputer controller 808. The computer controller 808 uses theinstructions to move the print head 802 through a series of momentsalong the surface 810 forming the reactor 812.

Referring now to FIG. 9, an embodiment of a system utilizing theinventor's reactor for (1) removing the target gas from a fluid ormixture and (2) for regenerating the reactor to remove the capturedtarget gas from the reactor and getting it ready for another cycle ofremoving target gas from a fluid or mixture. This embodiment isdesignated generally by the reference numeral 900.

The system 900 uses a stack 904 of reactors in cylindrical rectorvessels 902 a and 902 b for removing the target gas from a fluid ormixture. An example of using the reactor for removing a target gas froma fluid or mixture include use in the capture of carbon dioxide from gasmixtures containing carbon dioxide (examples: fossil fuel plants,natural gas streams, air). Also, the system 900 can be used for removingand/or capturing other gases including nitrous oxides (NOx), sulphates(SOx), hydrogen sulfide, or other trace gases.

The target gas in a fluid or mixture 906 is directed to one of thereactor vessels 902 a or 902 b. This is accomplished by selectivelyusing the valves 908 a and 908 b to channel the target gas in a fluid ormixture to the selected reactor vessel. The target gas in a fluid ormixture passes through the selected reactor stack and the reactivematerial in the reactor removes the gas. The fluid or mixture exits thesystem through valve 914 a or 904 b.

The reactors in the stack 904 of reactors needs to be purged of thetrapped target gas. This can be accomplished using the temperaturecontrol system 912 a and/or 912 b and the purge system 910 a and/or 910b. Once the reactors in the stack 904 of reactors have been purged ofthe trapped target gas they are ready for reuse. This is accomplished byselectively using the valves 908 a and 908 b to channel another targetgas in a fluid or mixture to the reactor vessel with the purgedreactors.

As illustrated in FIG. 10, another embodiment of the reactor isillustrated. This embodiment is designated generally by the referencenumeral 1000. The reactor 1000 includes individual channels 1002 formedby the shape of the structural members 1004. The structure is made ofmicron-scale domains of solid or liquid sorbent units 1006 embeddedwithin a gas-permeable polymer 1008 to form the monolith reactor 1000.The physical dimensions can be varied by length, width, and height. Asmaller filament size yields higher surfaced to volume ration and fasterabsorption rates. Temperature control tubes 1010 are in the structuralmembers 1004. The coolant tubes can be used for heat exchange and forrecycling the reactors.

Referring now to FIG. 11, an embodiment of a reactor stack isillustrated. This embodiment is designated generally by the referencenumeral 1100. A reactor vessel 1102 contains reactors in a reactor stack1104. Coolant tubes 1106 are in the individual reactors. The target gasin a fluid or mixture is directed through the reactor stack 1004 whereinthe stripping solvent in the individual reactors removes the target gas.

Additional Apparatus, Systems, and Methods Embodiments

The description above describes composite materials for carbon dioxidecapture that incorporate a carbon dioxide capture material into a gaspermeable polymer. As described, this composite can be 3-D printed ormanufactured by conventional means and can be used to remove carbondioxide from mixed or pure gas streams. The composite can also be usedto capture other gases. The composite material can be shaped to desiredreactor dimensions and can be tailored to have hierarchical structure toimprove gas flow, alter the pressure drop across the reactor, orincrease the rate of gas sorption. A higher composite surface area(exposed to the gas) results in a higher gas sorption rate. Theinventors have developed additional apparatus, systems, and methods forcarbon dioxide capture that incorporate a carbon dioxide capture forcarbon dioxide capture that utilize a carbon dioxide capture composite.

These composites are comprised of active materials for gas sorption(e.g. carbon capture chemicals) embedded within a gas permeable polymer.The active materials can be solids, liquids, encapsulated liquids, orsolid precursors to liquid solvents (e.g. dispersed as solid powdersthen rehydrated). The inventors' additional apparatus, systems, andmethods provide the carbon dioxide capture composite features identifiedand described below.

A carbon capture or other gas capture composite material that containstwo or more gas permeable polymers such that one of the polymers forms asealant coating around the other. This sealant polymer is less permeableto water migration and serves to prevent active materials from leachingout or contaminants from leaching in.

A carbon capture or other gas capture composite material that containstwo or more gas permeable polymers such that one or more polymers issignificantly less water permeable than the others. These polymers(along with the active material) are mixed together prior to shaping andcuring the composite. The significantly less water permeable polymerserves to prevent active materials from leaching out or contaminantsfrom leaching in.

A carbon capture or other gas capture composite material shaped as aseries of thin sheets which can be stacked in a reactor, rolled andinserted into a reactor, or crumpled and inserted into a reactor. Thehierarchical structuring controls gas sorption rates, gas flow-throughrates and pressure drop across the reactor.

A carbon capture or other gas capture composite material shaped as aseries of thin, porous or lace-like sheets which can be stacked in areactor, rolled and inserted into a reactor, or crumpled and insertedinto a reactor. The hierarchical structuring controls gas sorptionrates, gas flow-through rates and pressure drop across the reactor.

A carbon capture or other gas capture composite material shaped as arandomly entangled mass of filaments.

A carbon capture or other gas capture composite material where theembedded active (e.g. carbon capture) chemicals are at sufficientconcentration so as to exceed a percolation threshold within thecomposite, creating a network of continuous connectivity of the activechemicals. This material can be sealed with a second polymer to reduceleaching.

A manufacturing method where the composite is extruded from ahigh-pressure extruder. The high pressure is necessary for highlyviscous inks, generated with a high loading of carbon capture solids.The high-pressure extrusion can also tailor the radial distribution ofactive material within the composite filament by manipulating flowproperties.

A manufacturing method where the composite is extruded from ahigh-pressure extruder with local heating for in situ curing.

A manufacturing method where the composite is extruded from ahigh-pressure extruder with local UV light directed at the nozzle tipfor in situ UV curing.

A manufacturing method where the composite is cast, extruded or printedinto a mold. The mold can be of a sacrificial material.

A manufacturing method where the composite is coated with a secondpolymer during the extrusion process. This polymer can have greaterresistance to water migration and seal the exterior of the composite toprevent active materials from leaching out or contaminants from leachingin. This second polymer can be applied before or after the first polymerhas been cured. This second polymer can be cured concurrently orseparately from the curing of the first polymer. The second polymer ispermeable to some gases.

A manufacturing method where the composite is coated with a secondpolymer by spray coating after the composite has been shaped. Thispolymer can have greater resistance to water migration and seal theexterior of the composite to prevent active materials from leaching outor contaminants from leaching in. This second polymer can be appliedbefore or after the first polymer has been cured. This second polymercan be cured concurrently or separately from the curing of the firstpolymer. The second polymer is permeable to some gases.

A manufacturing method where after the composite has been shaped andcured, it is dipped into a second polymer to coat the composite. Thesecond polymer can have greater resistance to water migration and sealthe exterior of the composite to prevent active materials from leachingout or contaminants from leaching in. The second polymer can be cured ina separate step and is permeable to some gases. Prior to curing thesecond polymer, excess liquid can be blown off using localized gas flow.

A manufacturing method where an additional polymer coating is applied bypassing the composite through a layer of polymer that is floating on asecond immiscible fluid that does not interact with the composite.

A manufacturing method where the composite is rolled into a thin film

A manufacturing method where the composite is spread into a thin film bydoctor blading.

A manufacturing method where the composite is cast into a thin film byrapid spinning.

A manufacturing method where the composite is first formed into a thinfilm and then sliced into thin strips. The slicing can be concurrentwith the process of producing the thin film. For instance, rollers mayconcurrently roll the composite into a thin film and push it through aslicing apparatus.

A method of composite regeneration where room temperature air (or othergas) is blown through the composite to remove the absorbed carbondioxide (or other gas).

A method of composite regeneration where the composited is heated toremove the absorbed gases (with or without concurrent air flow).

A method of composite regeneration where hydrated air (or other gas) isblown through the composite to remove the absorbed carbon dioxide (orother gas). The hydrated air prevents the composite from losing watermass and drying out.

A method of operation where the gas stream to undergo sorption ishydrated to prevent the sorbet from drying out during the sorptionprocess.

A method of composite regeneration where steam (saturated orsuperheated) is flowed over the composite to remove absorbed gases.

A method of regenerating the composite with a pressure swing cycle,where absorption takes place during high pressure periods and desorptiontakes place during low pressure periods.

A method of operation where the composite is rehydrated after a fixednumber of cycles by soaking the composite in water.

A method of operation where the composite is rehydrated after a fixednumber of cycles by soaking the composite in a solution that isosmotically balanced to the composition of the fluid pockets inside ofthe composite prior to cycling.

A method of operation where the composite is rehydrated after a fixednumber of cycles by exposing the composite to water saturated vapor.

Referring now to FIG. 12 another embodiment of the inventor's reactor isillustrated. This embodiment is designated generally by the referencenumeral 1200. The reactor 1200 includes an extruded composite 1204 witha coating layer 1202. The coating layer 1202 can be a polymer coatingand in various embodiments the coating layer 1202 can be a gas-permeablepolymer coating. The extruded composite 1204 includes a solid or liquidreactive filler 1206 that functions as a gas sorbent or catalyst forchemical reactions as explained above. The solid or liquid reactivefiller 1206 of the extruded composite 1204 can include multiplecomponents. As illustrated in FIG. 12, the extruded composite 1204 canincludes units of sorbent material 1208. The units of sorbent material1208 can take many forms. For example, the units of sorbent material1208 can be units of carbon dioxide stripping material, units ofstripping material for stripping other gasses than carbon dioxide,liquid units of carbon dioxide stripping material, solid units of carbondioxide stripping material, solid droplets of carbon dioxide strippingmaterial encapsulated in capsules, or liquid droplets of carbon dioxidestripping material encapsulated in capsules. The reactor with a coatinglayer 1200 can be 3-D printed or manufactured by conventional means andcan be used to remove carbon dioxide from mixed or pure gas streams. Thereactor with a coating layer 1200 can also be used to capture othergases. The material can be shaped to desired reactor dimensions and canbe tailored to have hierarchical structure to improve gas flow, alterthe pressure drop across the reactor, or increase the rate of gassorption. A higher surface area (exposed to the gas) results in a highergas sorption rate.

Referring now to FIG. 13 an embodiment of the inventor's reactor as athin sheet rolled up is illustrated. This embodiment is designatedgenerally by the reference numeral 1300. The thin sheet rolled upreactor 1300 can be made using the extruded composite 1204 with acoating layer 1202 illustrated in FIG. 12. The extruded composite 1204includes a solid or liquid reactive filler 1206 and units of sorbentmaterial 1208. The thin sheet rolled up reactor 1300 can be 3-D printedor manufactured by conventional means and can be used to remove carbondioxide from mixed or pure gas streams. The thin sheet rolled up reactor1300 can also be used to capture other gases. The material can be shapedto desired reactor dimensions and can be tailored to have hierarchicalstructure to improve gas flow, alter the pressure drop across thereactor, or increase the rate of gas sorption. A higher surface area(exposed to the gas) results in a higher gas sorption rate.

Referring now to FIG. 14 an embodiment of the inventor's reactor as arandomly entangled mass of filaments 1402 is illustrated. Thisembodiment is designated generally by the reference numeral 1400. Therandomly entangled mass of filaments reactor 1400 can be 3-D printed ormanufactured by conventional means and can be used to remove carbondioxide from mixed or pure gas streams. The randomly entangled mass offilaments reactor 1400 can also be used to capture other gases. Thematerial can be shaped to desired reactor dimensions and can be tailoredto have hierarchical structure to improve gas flow, alter the pressuredrop across the reactor, or increase the rate of gas sorption. A highersurface area (exposed to the gas) results in a higher gas sorption rate.

Referring now to FIG. 15 an embodiment of the inventor's reactor as athin sheet of porous mesh-like or lace-like structure is illustrated.This embodiment is designated generally by the reference numeral 1500.The thin sheet of porous mesh-like or lace-like structure reactor 1500includes layers of individual filaments 1502. The thin sheet of porousmesh-like or lace-like structure reactor 1500 can be 3-D printed ormanufactured by conventional means and can be used to remove carbondioxide from mixed or pure gas streams. The thin sheet of porousmesh-like or lace-like structure reactor 1500 can also be used tocapture other gases. The material can be shaped to desired reactordimensions and can be tailored to have hierarchical structure to improvegas flow, alter the pressure drop across the reactor, or increase therate of gas sorption. A higher surface area (exposed to the gas) resultsin a higher gas sorption rate.

Although the description above contains many details and specifics,these should not be construed as limiting the scope of the applicationbut as merely providing illustrations of some of the presently preferredembodiments of the apparatus, systems, and methods. Otherimplementations, enhancements and variations can be made based on whatis described and illustrated in this patent document. The features ofthe embodiments described herein may be combined in all possiblecombinations of methods, apparatus, modules, systems, and computerprogram products. Certain features that are described in this patentdocument in the context of separate embodiments can also be implementedin combination in a single embodiment. Conversely, various features thatare described in the context of a single embodiment can also beimplemented in multiple embodiments separately or in any suitablesubcombination. Moreover, although features may be described above asacting in certain combinations and even initially claimed as such, oneor more features from a claimed combination can in some cases be excisedfrom the combination, and the claimed combination may be directed to asubcombination or variation of a subcombination. Similarly, whileoperations are depicted in the drawings in a particular order, thisshould not be understood as requiring that such operations be performedin the particular order shown or in sequential order, or that allillustrated operations be performed, to achieve desirable results.Moreover, the separation of various system components in the embodimentsdescribed above should not be understood as requiring such separation inall embodiments.

Therefore, it will be appreciated that the scope of the presentapplication fully encompasses other embodiments which may become obviousto those skilled in the art. In the claims, reference to an element inthe singular is not intended to mean “one and only one” unlessexplicitly so stated, but rather “one or more.” All structural andfunctional equivalents to the elements of the above-described preferredembodiment that are known to those of ordinary skill in the art areexpressly incorporated herein by reference and are intended to beencompassed by the present claims. Moreover, it is not necessary for adevice to address each and every problem sought to be solved by thepresent apparatus, systems, and methods, for it to be encompassed by thepresent claims. Furthermore, no element or component in the presentdisclosure is intended to be dedicated to the public regardless ofwhether the element or component is explicitly recited in the claims. Noclaim element herein is to be construed under the provisions of 35U.S.C. 112, sixth paragraph, unless the element is expressly recitedusing the phrase “means for.”

While the apparatus, systems, and methods may be susceptible to variousmodifications and alternative forms, specific embodiments have beenshown by way of example in the drawings and have been described indetail herein. However, it should be understood that the application isnot intended to be limited to the particular forms disclosed. Rather,the application is to cover all modifications, equivalents, andalternatives falling within the spirit and scope of the application asdefined by the following appended claims.

The invention claimed is:
 1. A method of making a reactor for removing asingle gas or multiple gases from a gas stream containing the single gasor the multiple gases, comprising the steps of: providing a fillermaterial, providing a sorbent material, extruding said filler materialand said sorbent material to produce an extrudant, and providing agas-permeable polymer coating layer around said extrudant to produce thereactor.
 2. The method of making a reactor for removing a single gas ormultiple gases from a gas stream containing the single gas or themultiple gases of claim 1 wherein said sorbent material includes unitsof sorbent material and wherein said units of sorbent material are unitsof carbon dioxide stripping material.
 3. The method of making a reactorfor removing a single gas or multiple gases from a gas stream containingthe single gas or the multiple gases of claim 1 wherein said sorbentmaterial includes units of sorbent material and wherein said units ofsorbent material are units of stripping material for stripping othergasses than carbon dioxide.
 4. The method of making a reactor forremoving a single gas or multiple gases from a gas stream containing thesingle gas or the multiple gases of claim 1 wherein said sorbentmaterial includes units of sorbent material and wherein said units ofsorbent material are liquid units of carbon dioxide stripping material.5. The method of making a reactor for removing a single gas or multiplegases from a gas stream containing the single gas or the multiple gasesof claim 1 wherein said sorbent material includes units of sorbentmaterial and wherein said units of sorbent material are liquid dropletsof carbon dioxide stripping material encapsulated in capsules.
 6. Themethod of making a reactor for removing a single gas or multiple gasesfrom a gas stream containing the single gas or the multiple gases ofclaim 1 wherein said sorbent material includes units of sorbent materialand wherein said units of sorbent material are solid units of carbondioxide stripping material.
 7. The method of making a reactor forremoving a single gas or multiple gases from a gas stream containing thesingle gas or the multiple gases of claim 1 wherein said sorbentmaterial includes units of sorbent material and wherein said units ofsorbent material are solid droplets of carbon dioxide stripping materialencapsulated in capsules.
 8. The method of making a reactor for removinga single gas or multiple gases from a gas stream containing the singlegas or the multiple gases of claim 1 wherein said sorbent materialincludes units of sorbent material and further comprising the step offorming said extrudant into a flat sheet of said extrudant with saidfiller in said extrudant, with said units of sorbent material in saidextrudant with said filler; and with said gas-permeable polymer coatinglayer around said extrudant.
 9. The method of making a reactor forremoving a single gas or multiple gases from a gas stream containing thesingle gas or the multiple gases of claim 1 wherein said sorbentmaterial includes units of sorbent material and further comprising thestep of forming said extrudant into a rolled sheet of said extrudantwith said filler in said extrudant, with said units of sorbent materialin said extrudant with said filler; and with said gas-permeable polymercoating layer around said extrudant.
 10. The method of making a reactorfor removing a single gas or multiple gases from a gas stream containingthe single gas or the multiple gases of claim 1 further comprising thestep of forming said extrudant into an entangled mass of filaments. 11.The method of making a reactor for removing a single gas or multiplegases from a gas stream containing the single gas or the multiple gasesof claim 1 further comprising the step of forming said extrudant into alayered mass of filaments.
 12. The method of making a reactor forremoving a single gas or multiple gases from a gas stream containing thesingle gas or the multiple gases of claim 1 further comprising the stepof forming said extrudant into a woven mass of filaments.